Color photographic light-sensitive materials

ABSTRACT

A color photographic light-sensitive material which comprises a support having thereon at least one silver halide emulsion layer containing a coupler represented by the following general formula (I)   wherein Q represents a coupler residue which can form a dye on reaction with an oxidation product of an aromatic primary amino developing agent; R1 represents an alkyl group, an aralkyl group, an alkoxy group, an alkoxyalkyl group, an acylamido group or an alkoxycarbonyl group, each having from 4 to 20 carbon atoms; R2 represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; m represents an integer of 1 to 4; n represents an integer of 1 to 4; and the sum of m + n is 2 to 5; and R1 and R2 can combine to form a non-metallic atom-containing five membered or six membered ring. These couplers have excellent solubility in coupler solvents and good stability to heat.

United States Patent 11 1 Arai et al.

[ COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS [75] Inventors: AtsuakiArai; Yasushi Oishi, both of Kanagawa, Japan [73] Assignee: Fuji PhotoFilm Co., Ltd.,

Kanagawa, Japan [22] Filed: June 18, 1974 [2]] Appl. No.: 480,456

[30] Foreign Application Priority Data June 20, 1973 Japan 48-69383 [52]US. Cl 96/100; 260/310 R; 260/562 R; 260/571 [5 l] Int. Cl G03c 1/40[58] Field of Search 96/100, 74

[56] References Cited UNITED STATES PATENTS 3,285,747 ll/1966 Coles96/100 3,737,3l8 6/1973 lnoue et al 96/100 Primary E.\'aminer.l. TravisBrown Anorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak[57] ABSTRACT A color photographic light-sensitive material which June24, 1975 comprises a support having thereon at least one silver halideemulsion layer containing a coupler repre sented by the followinggeneral formula (l) 3 (R Q NHCOC o (1) wherein 0 represents a couplerresidue which can form a dye on reaction with an oxidation product of anaromatic primary amino developing agent; R, represents an alkyl group,an aralkyl group, an alkoxy group, an alkoxyalkyl group, an acylamidogroup or an alkoxycarbonyl group, each having from 4 to 20 carbon atoms;R represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkylgroup having I to 5 carbon atoms or an alkoxy group having I to 5 carbonatoms; m represents an integer of l to 4; n represents an integer of lto 4; and the sum of m n is 2 to 5; and R and R can combine to form anon-metallic atom-containing five membered or six rnembered ring. Thesecouplers have excellent solubility in coupler solvents and goodstability to heat.

12 Claims, No Drawings 1 COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALSBACKGROUND OF THE INVENTION 1. Field of the Invention The presentinvention relates to a color photographic light-sensitive material. Moreparticularly, it relates to a color photographic light-sensitivematerial which contains a novel coupler having an aryloxyisobutyramidogroup, as an oleophilic group.

2. Description of the Prior Art In general, couplers having anoleophilic diffusionresistant group suitable for use in the productionof color photographic light-sensitive materials having good photographiccharacteristics need to fulfill the following properties.

1. Both the coupler and the dye formed therefrom by color developmentshould have a good solubility in a high boiling organic solvent (forexample tricresyl phosphate) which is employed to disperse the coupler.

2. The coupler should have good stability when incorporated into asilver halide photographic emulsion and provide a stable coating on asupport without deposition of the coupler.

3. The coupler should have good diffusion-resistance and should notdiffuse into other layers.

4. The coupler should have a high coupling reactivity and should producea dye image having good spectral absorption characteristics as well asgood stability to heat, humidity and light.

5. The coupler should be capable of being produced in high purity fromlow cost raw materials in a simple manner with good reproducibility.

For the purpose of improving the sharpness of color images, it isdesired to reduce the thickness of emulsion layers, and thus use of theleast amount as possible of a high boiling solvent for dispersing thecouplers is desired. It is also necessary to properly maintain thecoupler dispersion particles in a stable condition in order to improvethe coupling reactivity of coupler and the stability of the dye images.

Many investigations have hitherto been made on oleophilicdiffusion-resistant groups which are quite important in the developmentof an oil-soluble incorporated type coupler which fulfills theabove-described conditions.

ln conventional oil-soluble couplers represented by the followinggeneral formula (ll) 5 (II) Q NH C W wherein Q has the same meaning asdefined above, W represents a diffusion-resistant group, a group havingfrom 9 to 28 carbon atoms has been selected as a diffusion resistantgroup. When couplers having a group of less than 9 carbon atoms areused, because of their insufficient oil solubility anddiffusion-resistance, they partially dissolve into a developer solutionor diffuse from an emulsion layer in which they have been incorporatedto other layers to reduce the color reproducibility of the colorphotographic light-sensitive material. On the other hand, when couplershaving a group of more than 28 carbon atoms are used, due to theirincreased molecular weight, the extinction coefficient per unit weightor volume of the dyes formed is small. In addition, the solubility ofthe couplers per se decreases due to van der Waal attractive forcesbased on such a group, resulting in a large amount of organic solventbeing required and, disadvantageously, an increase in the thickness ofthe emulsion layers is required to obtain sufficient color density inthe emulsion layers.

As the substituent in the general formula (ll), a substituted orunsubstituted aliphatic acyl group, for example, l an n-tridecanoylgroup as described in the specification of Japanese patent ApplicationNo. 21,454/73 and (2) a B-(N-n-pentadecyl-n-butyramido)propionyl groupas described in the specification of Japanese Patent Publication No.2837/64, is known. As a diffusion-resistant group containing an aromaticring, for example, (3) a 2,4-di-tert.-amylphenoxyacetyl group asdescribed in the specification of U.S. Pat. Nos. 2,589,004 and2,600,788, (4) a 2,4-di-sec.-amylphenoxyacetyl group as described in thespecification of Japanese Patent Publication No. 3660/69, (5) an0r-(2,4-di-tert.- amylphenoxy)butyryl group as described in thespecification of U.S. Pat. No. 2,801 ,l7l, (6) an a (2-tetradecyl-4-chloro-S-methylphenoxy)butyryl group as described inspecification of German Offenlegungsschrift No. l,9l5,948, (7) a2,4-di-tert.-amyl-6-chlorophenoxyacetyl group as described in thespecification of German Offenlegungsschrift No. 2,028,601, and (8) a3-n-pentadecylphenoxyacetyl group as described in the specification ofU.S. Pat. No. 2,908,573 and British Pat. No. 852,922, and the like areknown.

Among them, a coupler containing diffusion-resistant group l due to itshigh aliphatic character, has insufficient solubility in a high boilingorganic solvent which is used as a solvent for dispersing an oil-solublecou pler. In particular, a benzoylacetoanilide type yellow coupler and aphenol type cyan couper containing such a group has poor couplerdispersion stability and often the deposition of coupler results. In thecase of a coupler containing diffusion resistant group (2 thepurification and crystallization of the coupler during preparation ofthe coupler are generally difficult. Many procedures are needed toobtain a coupler of high purity, and hence, this is not advantageousfrom the standpoint of cost. Further a coupler which contains as thediffusion-resistant group such a long alkyl group generally has a lowmelting point and is quite soluble in organic solvents at relativelyhigh temperatures, but has the disadvantages that the solubility dependsgreatly on the temperature and coupler is difiicult to dissolve inorganic solvents.

On the other hand, it is recognized that a coupler having anaryloxyalkylacylamido group is advantageous in that the solubility ofsuch a coupler in organic solvents tends to be less temperaturedependent. In addition, an emulsion layer containing such a coupler hasa high film strength and there is less movement of the coupler in anemulsion layer.

Diffusion-resistant groups (3), (4), (7) and (8) exhibit substantiallysimilar properties, and particularly cyan, magenta and yellow couplerscontaining diffusion-resistant group (3) are described in manyreferences as typical oil-soluble incorporated type couplers. Forexample. in the specification of US. Pat. No. 2,618,64l the followingcoupler examples (A, B and C) are described.

CouplerA (cyan) Cl I\HCOCH O-. )-C H (t) Coupler B (magenta) (t)H C-QOCH CO H- c a (t) colts-i3 N :8

\N/ Cl l Cl i CouplerC (yellow) However, these couplers have highmelting points, a tendency toward crystallization and insufticicientsolubility in conventional high boiling coupler solvents. Thus, due tocoupler deposition, a stable dispersion of the coupler in highconcentration is difficult to obtain.

Of these couplers, those having diffusion-resistant group (4) generallyhave low melting points. This is because the raw material.2,4-di-sec.-amylphenol, includes isomers which are introduced into thecoupler, and consequently isolation and purification of the coupler inhigh purity are difficult, resulting in decreasing the yield of thecoupler. On the contrary, in couplers having an oleophilic group inwhich an alkyl substituent is introduced into the (Jr-position of thealkylacyl group such as the diffusion-resistant groups (5) and (6) (ineach of (5) and (6) an ethyl group is introduced), solubility in organicsolvents is greatly improved, however,

the reaction between the a-halobutyric acid and phenol used in preparingthe coupler is not very sufficient in view of the yield obtained andthus this is not advantageous from an economical standpoint. 5 Further.the most disadvantageous characteristic which couplers containingdiffusion resistant groups (3) to (8) have is the dye images formed fromthese couplers by color development in multilayer color light-sensitivematerials in which these couplers are incorporated tend to have reducedheat stability. This is particularly marked in indophenol type dyeimages prepared from cyan couplers. These facts have been recognizedfrom detailed investigations on the heat stability of dyes formed fromvarious kinds of couplers and the influence of the couplers which existson the dyes, and, in addition, from comparison tests using photographicfilms which are prepared by dispersing couplers, coating the couplerdispersion on a support and drying. SUMMARY OF THE INVENTION An objectof the present invention is to produce color light-sensitive materialswhich have excellent photographic properties and color image stabilityusing couplers which have sufficient diffusion-resistance and highsolubility in high boiling organic solvents and for which a stabledispersion can be obtained and the thickness of layers can be decreaseddue to use ofa decreased amount of solvent, and which can be easilyprepared using readily available raw materials.

To improve stability of dye images is one of the most important problemsin the production of color lightsensitive materials and it is necessarynot only to improve the stability of the dyes per se which are formed bycolor development, but also to remove factors which promote the fadingof the dyes. Investigations in great detail have been made on theeffects due to the presence of other substances on the heat stability ofcolor developed dyes in a solution system and it has been found that theeffect of variations in the structure of couplers present is very greatand surprisingly that in a coupler which contains a substitutedphenoxyalkylacyl group as difi'usion resistant group. the structure ofthe NHCOCH CO- alkylacyl moiety of the group greatly influences the heatfading of the developed dyes.

As the results of various investigations, it has been discovered thatthe objects of the present invention can be accomplished by the use of acoupler having a new type of diffusion resistant group represented bythe general formula (I) described hereinafter, in anincorporated-coupler system in which a diffusion resistant coupler whichis insoluble or slightly soluble in water is dissolved in a high boilingpoint organic solvent which is immiscible with water and dispersed in aphotographic emulsion.

Accordingly this invention provides a color photographic light-sensitivematerial which comprises a support having thereon at least one silverhalide emulsion layer containing a coupler represented by the generalformula (I) Cll wherein 0 represents a coupler residue forming a dye onreaction with the oxidation product of an aromatic primary aminodeveloping agent; R, represents an alkyl group, an aralkyl group, analkoxy group, an alkoxyalkyl group, an acylamino group or an alkoxycarbonyl group, each having from 4 to 20 carbon atoms; R; represents ahydrogen atom, a chlorine atom, a hydroxy group, an alkyl group having lto 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; m is aninteger of l to 4; n is an integer of 1 to 4; and the sum of m n is 2 to5; and R and R may combine together to form a five-membered or a sixmembered nonmetallic atom containing ring.

DETAILED DESCRIPTION OF THE INVENTION Q in the general formula (I) canbe a phenol or a naphthol coupler residue containing a phenolic hydroxygroup, a pyrazolone, a cyanoacetophenone or an acylacetonilide couplerresidue containing an active methylene group, or a derivative thereof inwhich the active position is substituted (the so called twoequivalenttype coupler). When Q is a phenol or naphthol compound, the coupler is acyan dye forming cou- A pler; when Q is a pyrazolone or acyanoacetophenone compound, the coupler is a magenta dye formingcoupler, and when Q is an acylacetoanilide compound the coupler is ayellow dye forming coupler. Examples of m i ty are as follows:

- O CH R 0 CH R G-CH R, C \Q o 0 R O O etc 3 f C\ C C 2 R such couplerresidues are residues of the couplers disclosed in the following U.S.Patents.

Yellow: U.S. Pat. Nos. 3,277,155; 3,415,652; 3,447,928; 3,408,194;2,875,057; 3,265,506; 3,409,439; 3,551,155; 3,551,156; 3,582,322, etc.

Magenta: U.S. Pat. Nos. 2,600,788; 2,983,608; 3,006,759; 3,062,653;3,214,437; 3,253,924; 3,311,476; 3,419,391; 3,419,808; 3,476,560;3,582,322, etc.

Cyan: U.S. Pat. Nos. 2,474,293; 2,698,794; 3,034,892; 3,214,437;3,253,924; 3,311,476;

3,458,315; 3,582,322; 3,591,383; etc,

It is preferred from a synthetic standpoint that R, and R: be positionedat the 3- and 5-positions on the phenoxy ring. When R, and R areconnected together to form a ring, they are preferrably positioned atthe 3- and 4-positions of the phenoxy ring as shown in the followingformula:

wherein A, i.e., the combinations of R, and R represents a divalentgroup necessary to form a S-membered or 6-membered ring, and which cancontain one or more oxygen atoms together with carbon atoms.

For A, a divalent group having from 2 to about 35 carbon atoms, forexample, those represented by the following formula are preferred:

wherein B represents CH- or O; R R,, R and R., each represents ahydrogen atom or an alkyl group having 1 to 20 carbon atoms, and prepresents 0 or 1.

Specific examples of the For diffusion resistance, the total number ofcarbon atoms contained in the moiety 9 5 (R macoo 0 CH5 2 m is suitablyfrom about 14 to 42, and preferably from 18 to 32.

In the present invention, as the coupling residue for Q the followingresidues are particularly preferred.

13 @wocacozm F c- COCHCONH R12 CH3 X Y w ca e-cosmonaca x CIII-CH-Xwherein R represents a mono-valent atom or group, such as a hydrogenatom, a halogen atom, an alkyl group, an alkoxy group, an amino group,an acylamino group; R. represents a hydrogen atom or a monovalent groupattached to the 3-, 4- or 5-position of the anilide ring, such as ahalogen atom, a cyano group, a carbamoyl group, an alkoxycarbonyl group,a sulfamoyl group, an acylamino group, a nitro group, an alkyl group, anaryl group, an alkoxy group, an aryloxy group, an imido group, analkylsulfonyl group, an arylsulfonyl group, etc.; R represents an arylgroup, particularly a phenyl group substituted with a halogen atom, analkyl group, an alkoxy group, an aryloxy group, a nitro group, a cyanogroup, an acylamino group, etc.; R represents one or more mono-valentatoms or groups, such as a hydrogen atom, a halogen atom, an alkylgroup. an alkoxy group, an aryloxy group, etc.; R represents amono-valent group, such as an alkyl group, an aryl group, an alkoxygroup, a carbamoyl group, an acylamino group, an ureido group, ananilino group, or an alicyclicamino group, etc.; R represents one ormore mono-valent atoms or groups, such as a halogen atom, an alkylgroup, an alkoxy group, an aryloxy group, or an acylamino group, etc.; Rrepresents a mono-valent atom or group, such as a hydrogen atom, analkyl group, an aryl group, etc.; R represents a di-valent group, suchas an alkylene group. an arylene group, etc.; X represents a hydrogenatom or a coupling-off group which splits off on coupling with theoxidation products of an aromatic primary amino developing agent, forexample. such as a halogen atom, an alkoxy group. an aryloxy group, anacyloxy group, a sulfonyl group, an arylthio group, a heterocyclicthiogroup, a cyclic imido group, an arylazo group. a cyclicsulfonylacylamino group. etc.; Y represents a hydrogen atom, a halogenatom, an alkyl group, an alkoxy group, an aryloxy group, aN,N-dialkylamino group, etc.

The couplers represented by the general formula (I), which can be usedin the present invention, can be prepared easily and in high yield bythe reaction of an amino compound represented by the general formula(III):

NH- Q wherein O has the same meaning as defined above, with anappropriate acid chloride derived in conventional manner from ana-(substituted phenoxy)isobutyric acid represented by the generalformula (IV):

(R ca (IV) 2 m -o-%-cooa wherein R R. m and n have the same meaning asdefined above.

Further, the yellow two-equivalent couplers and the magentatwo-equivalent couplers illustrated as examples can be prepared from thecoresponding fundamental couplers according to the methods such as thosedescribed in the specifications of US. Pat. Nos 3,447,928; 3,408,l94;and 3,265,506, German Offen- Iegungsshrift Nos. 2,213,461; and2,263,875.

The substituted phenoxy isobutyric acids represented by the generalformula (IV), such as, for example, w(4-nonylphenoxy )isobutyric acid,a-( 3-n-dodecyoxyphenoxy )isobutyric acid, a-( 4-ethoxyoctylphenoxy)isobutyric acid, a-( 3-n-pentadecylphenoxy )isobutyric acid, and 01-( 3-pentadecyl-4- chlorophenoxy )isobutyric acid, a-( 3 pentadecyl-4-methoxyphenoxy)isobutyric acid,a-(2-methyl-2-nhexyadecylchromanyl-fi-oxy)isobutyric acid,a-(2-noctadecyl-Z,3-dihydrobenzofuranyl-5-oxy)isobutyric acid, etc. arenovel compounds. They can be prepared in high yield in a one stepreaction according to the method described in M. Julia Bull. Soc. Chim.France, 1956, 776, in which the corresponding substituted phenol isheated with acetone and chloroform in the presence of an alkali metalhydroxide to form the alkali metal salt of the carboxylic acidrepresented by the general formula (IV), followed by neutralization witha mineral acid such as hydrochloric acid.

Specific examples of couplers which can be used in the present inventionare illustrated below, but these are only examples of couplersrepresented by the general formula (I) described above and are not to beconsidered as limiting the invention.

Coupler I a-( 4-Methoxybenzoyl)-2-chloro-5-{ a-(4-tert.-amylphenoxy)-isobutyramidol acetanilide Coupler IIa-Benzoyl-2-methoxy-5- {a-( 4-nonylphenoxy )isobutyramido} -acetanilideCoupler III a-( 4-Methoxybenzoyl )-2-chloro-5-{rx-( 3-n-pentadecylphenoxy)isobutyramido}acetanilide Coupler IV a-(Z-Methoxybenzoyl )-a-acetoxy-2-chloro-5- a-( 3- n-pentadecylphenoxy)isobutyramido}acetanilide Coupler V a-( 4-Methoxybenzoyl)-a-(4-carboxyphenoxy )-2- chloro-5-{a-( 3-n-pentadecylphenoxy)isobutyramido}acetanilide Coupler VIa-(4-Methoxybenzoyl)-oz-N-phthalimido)-2-chloro- 5-{a-(3-n-octyloxyphenoxy )isobutyramido} acetanilide Coupler VIIoz-Pivaloyl-Z-chloro-S- {a-(4-tertamylphenoxy )isobutyramidolacetanilide Coupler VIII a-PivaloyI-a--{-4-(4-benzyloxyphenylsulfonyl)phenoxy} -2-chloro-5- {a-(tert.-amylphenoxy)isobutyramidol acetanilide Coupler IXa-Iivaloyl-2-chloro-5- a( 3-pentadecylphenoxy)isobutyramidolacetanilideCoupler X a-Pivaloyl-a-( lethylcarbamoylphenylthio )-2-chloro-5-{-a-(3-n-pentadecylphenoxy)isobutyramido}acetanilide Coupler XIa-Pivaloyl-a-( 5 ,5-dimethyl-3-hydantoin y] )-2- methoxy-S- {a-(3-n-pentadecylphenoxy )isobutyramido) acetanilide Coupler XIIa-Pivaloyl-oz-( 2-benzotriazolyl)-2-chloro-5- {a-( 4- ethoxybutylphenoxy)isobutyramido} acetanilide Coupler XIII a-PivaIoyl-a-( 2,4-dioxo-5,5-dimethyl-3- oxyazolydinyl )-2-chIoro-5- {oz-( 3-n-pentadecylphenoxy)isobutyramido} acetanilide Coupler XIV a-PivaloyI-a-(l-phenethyl-3-hydantoinyl )-2- methoxy-5-a-(4-nonylphenoxy)isobutyramidoacetanilide Coupler XV a- {a-( 4-Tolyloxy )isobutyryl -2-chlor0-5- (a-(3 -npentadecylphenoxy( isobu tyramido Iacetanilide Coupler XLIV 1-Hydroxy-4-iodo-2-l N-[4-{a-(3-n-pentadecylphenoxy)isobutyramidolbenzyl] lnaphthamide Coupler XLV 2-{a-( 3-n-Pentadecyl-4- chlorophenoxy )isobutyramido }-4,6-dichloro-5-methylphenol Coupler XLVI 1-( 2,4.6-Trichlorophenyl )-3- {01-( 3n-pentadecyl-4- methoxyphenoxy )isobutyramido }-5-pyrazolone CouplerXLVll 2-{ a-( 2-Methyl-2-n-hexadecylchromanyl-6- oxy )isobutyramido)-4.6-dichloro-5-methylphenol Coupler XLVIII1-(2,6-Dich1oro-4-methoxyphenyl)-3-[3-{oz-(3-npentadecyl-4-hydroxyphenoxy)isobutyramidolbenzamidol-S-pyrazoloneCoupler XLIX SYNTHESIS EXAMPLE 1 Synthesis ofa-(4-Methoxybenzoyl)-2-chloro-5-{a- (3-n-pentadecy1phenoxy)isobutyramido lacetanilide (Coupler III) A crude product,a-(B-n-pentadecylphenoxy)isobutyric acid chloride obtained by thereaction of 19.5 g of a-(B-n-pentadecylphenoxy)isobutyric acid and 18 gof thionyl chloride in the presence of a catalytic amount ofdimethylformamide (0.5 g of DMF in 55 of benzene) in benzene, and 15.9 gof 01-(4- methoxybenzoyl)-2-chloro-5aminoacetanilide were reacted byheating in a solvent mixture of 40 ml of acetonitrile and 40 ml of ethylacetate for 6 hours. After some solid material was removed byfiltration, the liltrate was concentrated under reduced pressure, andthe residue was recrystallized from a solvent mixture of acetonitrileand ethyl acetate (3:1 by volume) to give 27.0 g of Coupler Ill ascolorless crystals with a melting point of 92C.

Found: C: 71.25 percent, H: 7.79 percent, N: 4.06 percent Calculated forC H,-, -,O -,N Cl: C: 71.13 percent, H: 8.03 percent. N: 3.73 percentSYNTHESIS EXAMPLE 2 Synthesis of a-Pivaloyl-Z-chloro-S- {a-(3-npentadecylphenoxy)-isobutyramido} acetanilide (Coupler IX) 53.7 g ofa-pivaloyl-Z-chloro-5-aminoacetanilide and an acid chloride prepared ina manner similar to that described in Synthesis Example 1 from 80 g ofa-( 3-npentadecylphenoxy)isobutyric acid were reacted by heating in asolvent mixture of 100 ml of acetonitrile and 60 ml of ethylene chloridefor 5.5 hours. After treating in a manner similar to that described insynthesis Example 1, the crude product was recrystallized from petroleumether to give 105 g of Coupler IX as colorless crystals with a meltingpoint of 7375C.

Found C: 71.19 percent, H: 390 percent, N: 4.37 percent Calculated forC;,,,H,-,;O,N- -Cl: C: 71.06 percent. H: 9.08 percent, N: 4.61 percentSYNTHESIS EXAMPLE 3 Synthesis of a-Pivaloyl-cx-( l-phenethyl-3-hydantoinyl)-2-methoxy-5- {a(4- nonylphenoxy)isobutyramido acetoanilide(Coupler XIV) Into a solution containing 1 1.0 g of a-pivaloyl-2-methoxy-5-{a-(4- nonylphenoxy)isobutyramido acetanilide dissolved in 100ml of chloroform; was added with stirring at 15C a solution containing3.3 g of bromine dissolved in 20 ml of chloroform, and reacted for 30minutes. The reaction mixture was washed twice with 30 ml of cold water,and then to the reaction mixture were added 6.0 g ofN-phenethylhydantoin and 3.2 g of triethylamine and the reaction mixturewas refluxed on a water bath for 6 hours. The reaction mixture waswashed with water and concentrated under reduced pressure. The residuewas recrystallized from a solvent mixture of petroleum ether andacetonitrile to give 5.7 g of Coupler XIV as white crystals with amelting point of 8285C.

Found: C: 70.12 percent. H: 7.73 percent, N: 7.39 percent Calculated forC,,H,-,,,O;N,: C: 70.03 percent H: 7.69 percent, N: 7.43 percentSYNTHESIS EXAMPLE 4 Synthesis of l-(2.4,6-Trichlorophenyl)-3-l3-{(Jr-(4tert-amylphenoxy )isobutyramido} benzamidol-S- pyrazolone (Coupler XXIV)40.0 g of l-(2,4,6-trichlorophenyl)-3-(3-aminobenzamido)-5-pyrazoloneand an acid chloride prepared in a manner similar to that described inSynthesis Example 1 from 25.0 g of a-(4terL-amylphenoxy )isobutyric acidwere refluxed in a solvent mixture of ml of acetonitrile and 40 ml ofethylene chloride for 6 hours. After removing some solid material byfiltration. the filtrate was concentrated under reduced pressure. Intothe residue. 20 g of sodium acetate and 40 ml of acetic acid weredissolved, the solution was poured into ice water with stiring and thecrystals are collected by filtration. The crude crystals wererecrystallized by a solvent mixture (3:1 by volume) of acetonitrile andethyl acetate to give 37.7 g of Coupler XXIV as colorless crystals witha melting point of 142143C.

Found: C: 58.77 percent, H: 5.37 percent, N: 8.36 percent Calculated forC;,,H:;1O,N CL;,: C: 59.09 percent, H: 4.92 percent, N: 8.90 percentSYNTHESIS EXAMPLE 5 Synthesis of 1-( 2,4,6-Trichlorophenyl )-3-[ 3- {a-(3-npentadecylphenoxy-isobutryamidolbenzamido]-5- pyrazolone (CouplerXXV) 20.0 g of1(2.4,6-trichlorophenyl)-3-(3-aminobenzamido)-5-pyrazolone and an acidchloride prepared in a manner similar to that described in SynthesisExample 1 from 12.5 g of u-(Ln-pentadecylphenoxy)isobutyric acid wererefluxed in a solvent mixture of 40 ml of acetonitrile and 40 ml ofethylene chloride for 5.5 hours. The reaction mixture was treated in amanner similar to that described in Synthesis Example 4. The crudeproduct was recrystallized from ethanol to 15 give 17.2 g of Coupler XXVas colorless crystals with a melting point of l37l38C.

Found: C: 63.87 percent. H: 6.65 percent. N: 7.25 percent Calculated forc.,H.,.o.N.c|.,; C: 63.94 percent. H: 6.63 percent. N: 7.28 percentSYNTHESIS EXAMPLE 6 Synthesis of l-(2,4.6-Trichlorophenyl)-3-[2-chloro--{a-(3-n-pentadecyl-phenoxy)isobutyramido} anilino]-5-pyrazolone(Coupler XXVlll) 23.0 g of l-(2.4,6-trichlorophenyl)-3-{(2-chloro-5-amino)anilino}-5-pyrazolone and an acid chloride prepared in a mannersimilar to that described in Synthesis Example I from 19.8 g ofa-(3-n-pentadecylphenoxy)isobutyric acid were refluxed in l ml ofacetonitrile for 3 hours. The reaction mixture was treated in a mannersimilar to that described in Synthesis Example 4. The crude product wasrecrystallized from a solvent mixture of acetonitrile and hexane (l:2 byvolume) to give 28.5 g of Coupler XXXVI" as colorless crystals with amelting point of l03105C. Found: C: 6l .98 percent. H: 6.39 percent, N:7.l8 percent Calculated for C..,H.-,..O;.N Cl C: 6l .86 percent. H: 6.44percent. N: 7.22 percent SYNTHESIS EXAMPLE 7 Synthesis of 2-{a-(4-tert.-Amylphenoxy )isobutyramido }-4.6-dichloro-5- methylphenol (CouplerXXXIX) 22.8 of 2-amino-4.6-dichloro-S-methylphenol hydrochloride and anacid chloride prepared in a manner similar to that described inSynthesis Example I from 25.0 g of a-(4-tert-amylphenoxy)isobutyric acidwere refluxed in a solvent mixture of 70 ml of acetonitrile and 40 ml ofethylene chloride for 4 hours. After removing some solid material byfiltration, the filtrate was concentrated to half volume and crystalswere collected. The crude crystals were recrystallized from acetonitrileto give 37.0 g of Coupler XXXIX as colorless crystals with a meltingpoint of l53l 64C.

Found: C: 62.23 percent. H: 6.60 percent, N: 3.24 percent Calculated forC H O NCl- C:62.26 percent. H: 6.37 percent. N: 3.30 percent SYNTHESISEXAMPLE 8 Synthesis of 2-{a-(3-n-Pentadecylphenoxy)isobutyramido}-4.6-dichloro-5- methylphenol (CouplerXL) Found: C: 68.05 percent. H: 8.24 percent. N: 2.43 percent Calculatedfor IlZ J2 IK 'J: I 68-09 percent. 8.33 percent. N: 2.48 percent 5 Ascan be seen from the above Synthesis Examples.

the couplers which can be used in the present invention are especiallyadvantageous from an economical standpoint in that they can be preparedin a simple manner and a good reproducibility by reacting a novela-(subl0 stituted)isobutyric acid hydrochloride. which can be preparedin highly purity and high yield by reacting an easily availablesubstituted phenol with acetone and chloroform in the presence of analkali metal hydroxide. with a yellow. magenta or cyan color couplerresidue containing an amino group.

The couplers which can be used in the present invention are a novelclass ofcompounds. and in comparison with a similar series of couplershaving diffusion resistant groups l to (8) including the known acylamide0 group described hereinbefore. they have a low melting point andexcellent solubility in a high boiling (e.g.. above l75C) organicsolvent and thus stable emulsion layer can be obtained without thedeposition of coupler crystals in the emulsion layer when they aredispersed 5 in a silver halide photographic emulsion and coated on asupport and dried. Due to such characteristics, it is possible togreatly reduce an amount of the high boiling solvent needed fordispersion, which is extremely advantageous for improving the imagesharpness of images. Further. while a coupler having a straight chainalkylacyl group (for example Comparative Coupler J describedhereinafter) has a very low melting point but shows a low solubility atlow temperature due to the high temperature dependency of the solubilityand hence tends to be deposited at low temperature, the couplersaccording to the present invention do not have such disadvantages andfurthermore they are characterized by less temperature dependence ofsolubility as compared with a similar series of couplers.

Using a series of phenolic cyan couplers represented by the generalformula (v). the melting points and the soiubilities in ethyl acetate at20C of the couplers of the present invention and comparison couplers areillustrated below. The comparison couplers have the same structure asthe couplers of the present invention except for the diffusion resistantgroups. and were pre- -pared according to the method described in USPat.

Nos. 2,801.17] and 2,908,573.

22.8 g of 2-amino-4,6-dichloro-S-methylphenol hy- OH drochloride and anacid chloride prepared in a manner I similar to that described inSynthesis Example I from C 39.0 g of a-(3-n-pentadecylphenoxy)isobutyricacid Nhco w were refluxed in l20 ml of acetonitrile for 7 hours. TheGeneral Formula (2') reaction mixture was treated in a manner similar tothat CH described in Synthesis Example 7. The crude product 3 I wasrecrystallized from acetonitrile to give 41.0 g of C1 Coupler XL ascolorless crystals with a melting point of Coupler Diffusion ResistantMelting Solubility in Group W Point Ethyl Acetate at 20C (Cl (WW/F) A CH-O C -.H,,(t) 15s 1.3

Continued Coupler Difl'usion Resistant Melting Solubility in Group WPoint Ethyl Acetate at 20C ("Cl (wt%) E 3 D -CHO C,-.H, (l) lSl-l52 20.0

5 "n m E -CH- CH -O Q C,-,Hi (l) 119-120 175 F CHgCH- -CH1-O C,-,H||(t)l24-l25 29.5

G CH O 129-[30 2.1

31 IE H c|-| 0 Q 70 32.5

1 5 3I J (CH 2CH;; 76 24.3

C IS Coupler XL of the C0 73 44,0

Present i invention C :1

Furthermore it has been recognized that the dye images formed by colordevelopment in a conventional manner of color light-sensitive materialsprepared using the couplers of the present invention have markedlysuperior heat stability as compared with those formed from knowncouplers having the above described diffusion resistant groups. Thisfact is a discovery would not be predicted from the known art, and is tobe noted (as shown in Example 4).

Also the melting points of typical yellow and magenta couplersrepresented by the general formula (I) which Structures and MeltingPoint ("C) of Typical Yellow and Magenta Couplers Difl-usion ResistantGroup W Known Group Invention Group QNHCO CH -O C Hn(t) CHO C.-.Hu(t) H(r) 5 ll C H ('l C H 3 i n) Coupler K Coupler L Coupler lll (H O Q-COCH. .CONH I33 110 92 HCO- CH" Cl Coupler M Coupler N Coupler IXCH;.-(I--COCH' 'CONH [37-438 88 90 73-75 Continued Structures andMelting Point (C) of Typical Yellow and Magenta Couplers DiffusionResistant Group W Known Group Invention Group CO O-NHCO -CH O C,H ,(tlCH() Q C,-,H,,tt)

H it) S 2 C H (n CH;-C-NHCO O Coupler B Coupler O Coupler XXV HCO- Nl77-l78 l4l-l42 l37-l38 Cl Cl Coupler P Coupler Q Coupler XXVlll CH- NHNHCO- Cl ,Cl Cl As can be seen from the results in the above table,

the couplers of the present invention have in common lower meltingpoints as compared with the comparison couplers 0f the homologousseries, and stable and very fine dispersions can be obtained even whenthe dispersion is prepared under the conditions of a reduced amount ofthe high boiling organic solvent. The coatings prepared under suchconditions can also provide dye images of transparency and clear colorhue by color development as will be seen in the Examples set out below.

The couplers of the present invention can be incorporated into ahydrophilic colloid of photographic materials using any known technique.For example, the coupler can be dissolved in a high boiling (e.g., above175C) solvent such as dibutyl phthalate, tricresyl phosphate ortrihexylphosphate as described in, e.g., U.S. Pat. No. 2,322,027together with, ifdesired, a subsidiary solvent such as ethyl acetate,tetrahydrofuran acetophenone, isopropyl acetate, ethyl propionate,B-ethoxyethyl acetate, n-butyl carbitol acetate, etc., and then thesolution is dispersed in a hydrophilic colloid binder.

Also. a coupler solution can be prepared using only the subsidiarysolvent without using the high boiling solvent and the solution can bedispersed in a hydrophilic colloid binder.

The coupler dispersion prepared in the manner illustrated above is mixedwith a silver halide emulsion such as a silver bromide, silveriodobromide, silver chloroiodobromide, silver chloride, silverchlorobromide or silver iodide emulsion or a so-called conversion halidetype silver halide emulsion as described in British Pat. No. 635,841 andU.S. Pat. Nos. 2,592,250 and 3,622,3 l8, and together with, if desired,an additional hydrophilic colloid binder and then the mixture is appliedto a support.

The dispersion of at least one coupler of the present invention and, ifdesired. in combination with at least one known coupler which is notwithin the scope of the couplers of the present invention, in ahydrophilic colloid binder which is prepared by the above describedmethod can be used as a component of at least one emulsion layer of amulti-layer silver halide photographic material which is based on thethree color subtractive system and which has at least one bluesensitivesilver halide emulsion layer containing a yellow dye forming coupler, atleast one green-sensitive silver halide emulsion layer containing amagenta dye forming coupler and at least one red-sensitive silver halideemulsion layer containing a cyan dye forming coupler. As the emulsionsfor the multi-layer photographic material, any known silver halideemulsion can be advantageously used, for example, such as thosedisclosed in U.S. Pat. Nos. 3,582,322; 3,622,3 l 8; 3,547,640;3,672,898; 3,516,83l; 3,7l5,208; 3,737,3 l2, 3,705,803; 3,705,799;3,703,375; 3,379,529; 3,402,046; 3,620,747; 3,450,536; 3,726,681; U.S.patent applications Ser. No. 206,060, filed Dec. 8, I97]; and Ser. No.259,l09, filed June 2, 1972.

As a support to which the emulsion layer containing the dye formingcoupler of the present invention is applied, any known support which canbe used for conventional photographic materials can be appropriatelyused. These include a cellulose ester film such as cellulose nitrate,cellulsoe acetate, etc., a polyester film such as polyethyleneterephthalate, etc., a polyvinyl chloride film, a polystyrene film, apolycarbonate film, a paper, a so-called baryta coated paper which isprepared by coating a barium sulfate layer on a paper support, a filmwhich is prepared by laminating a cellulose ester, polyester, polyvinylchloride, polystyrene or polycarbonate on a paper or a baryta coatedpaper, a synthetic paper, etc. A suitable coating amount of the coupleris about X to about l X 10 mol/m", preferably 2 X 10 to 3 X 10 mol/m andfor the silver halide a suitable coating amount ranges from about 5 X 10to about 1 X 10 mol/m preferably 2 X 10 to 3 X 10 mol/m'-.

As the hydrophilic colloid which can be used in the coupler dispersionof the present invention and the above described emulsion layer ofphotographic materials, for example, gelatin. a gelatin derivative(acylated gelatin. graft gelatin, etc.). albumin, gum arabic, agar agar,cellulose derivative (acetyl cellulose, hydroxyethyl cellulose,carboxymethyl cellulose. etc.), a synthetic resin (polyvinyl alcohol,polyvinyl pyrrolidone, polyacrylamido, etc.), and any other knownhydrophilic colloid can be employed.

The dispersion containing the coupler of the present invention in theabove described hydrophilic colloid or a mixture of the dispersion and asilver halide emulsion can be subjected to treatment under reducedpressure or washed with water as described in U.S. Pat. Nos. 2,949,360and 3,396,027 prior to coating of the emulsion layer of the abovedescribed photographic material for removing the subsidiary solvent.

Furthermore, in a step of dissolving the couplers of the presentinvention, which preceeds the step of dispersing the solution into ahydrophilic colloid binder, the dissolution of the coupler can befacilitated, if desired, using heat or ultrasonic waves as is known inthe art.

The above described multi-layer photographic material which includes thecouplers of the present inven tion can have, in addition to the abovedescribed silver halide emulsion layers, other layers conventionallyemployed in light-sensitive materials, for example, a protective layer,a filter layer, an intermediate layer, an anti-halation layer, a subbinglayer, a backing layer, a layer containing an ultraviolet absorber, etc.Also, as the binders for these layers, the hydrophilic colloid used forthe above described emulsion layers can be used.

Each layer of the above described material containing the coupler of thepresent invention can further contain a known compound as a hardeningagent for the hydrophilic colloid, for example, as described in C. E. K.Mees & T. H. James, The Theory oft/1e P11010- grap/zic Process, 3rd Ed.,pp. 5560, Macmillan, New York (1966), US. Pat. Nos. 3,316,095;3,232,764;

3,091,537; 3,321,313 and 3,543,292; British Pat. Nos. 974,723; 994,869and 1,167,027; etc. Typical examples examples are aldehyde typecompounds such as formaldehyde, glyoxal, succinaldehyde, glutaraldehyde,2,3-dihydroxy-l,4-dioxane, mucochloric acid, dimethylolurea, etcs,active vinyl type compound such as divinyLsulfone, methylenebismaleimide, 5-acetyl- 1,3-diacryloyl- 1 ,3,5-hexahydrotriazine, N,N,Ntriacryloyl-l,3,5-hexahydrotriazine, etc.; active halogen type compoundssuch as 2,4-dichloro--oxytriazine sodium salt,2,4-dichloro-6-methoxytriazine, sebacic acid bischloromethyl ether, N,N-bis( achloroethylcarbamoyl)piperazine, etc.; epoxy type compounds suchas bis( 2,3-epoxypropyl)methyl propyl ammonium para-toluene sulfonate,1,4-bis(2,3'-

22 epoxypropuloxy)butane, 1,3-diglycidyl-5-(y-acetoxy-B-oxypropyl)-isocyanurate, etc.; ethyleneimine type compounds such as2,4,6-triethyleneimino-l ,3,5- triazine, bis-B-ethyleneiminoethylthioether, etc.; methane sulfonic acid ester type compounds such asl,2-di(methanesulfonyloxy )ethane, 1,4-di(methanesulfonyloxy)butane,l,5-di(methanesulfonyloxy)pentane, etc.

The emulsion which can be used in the light-sensitive materialcontaining the coupler of the present invention can be chemicallysensitized using the natural sensitizers in gelatin or using a sulfurcompound as described in U.S. Pat. Nos. 1,574,944; 1,623,499 and2,410,689, Also, the emulsion can be sensitized with a salt of a noblemetal such as palladium, gold, ruthenium, rhodium, platinum, etc., asdescribed in US. Pat. Nos. 2,448,060; 2,399,083 and 2,642,361. Furtherthe emulsion can be sensitized with a reducing agent such as a stannoussalt as described in U.S. Pat. No.

2,487,850. The emulsion can also be sensitized with a polyalkylene oxidederivative as described in U.S. Pat. Nos. 2,886,437; 3,046,134;2,944,900 and 3,294,540. Moreover, the emulsion can be spectrallysensitized with a sensitizing dye, such as a cyanine dye or amerocyanine dye, as disclosed in U.S. Pat. Nos. 2,526,632; 2,503,776;2,493,748; 3,384,486; 2,933,390; and 2,937,089.

The emulsion can contain a stabilizer such as a mercury compound, anazaindene, etc., as described in U.S. Pat. Nos. 2,131,038; 2,694,716;2,886,437; 2,444,605; 2,728,663; 3,287,135; 3,236,652; 2,403,927;3,266,897; 3,397,987; 2,839,405;

3,220,839; 2,566,263; and 2,597,915; a plasticizer such as glycerine,etc., as described in U.S. Pat. Nos. 2,960,404; 2,588,765 and 3,121,060;and British Pat No. 955,061 and a coating aid such as saponin,polyethylene glycol monolauryl ether, etc., as described in U.S. PatNos. 2,600,831; 3,133,816 and 3,666,478. Further the emulsion cancontain an antistatic agent as described in U.S. Pat. Nos. 2,861,056;3,206,312; and 3,428,451, an ultraviolet absorber as described in U.S.Pat. Nos. 3,253,921; 2,739,971; 2,739,888; and 3,250,617, a fluorescentwhitening agent as described in U.S. Pat. Nos. 2,933,390; and 3,406,070,an antiirradiation dye as described in U.S. Pat. Nos. 3,253,921;2,274,782; 2,527,583; and 2,956,879, etc.

In the light-sensitive material containing the coupler of the presentinvention any known couplers in addition to the couplers of the presentinvention can also be used. For example, as a yellow dye forming couplerthere are the open chained ketomethylene type couplers and typicalexamples of such couplers are acylacetamide type couplers such as thebenzoylacetanilides and the pivaloylacetanilides, etc., as desclosed inU.S. Pat. Nos. 3,277,155; 3,415,652; 3,447,928; 3,408,194; 2,875,057;3,265,506; 3,409,439; 3,551,155; 3,551,156; 3,582,322, etc. As a magentadye forming coupler, there are pyrazolone type couplers, indazolone typecouplers, pyrazolobenzimidazole type couplers, cyanoacetyl typecouplers, etc., as disclosed in U.S. Pat. Nos. 2,600,788; 2,983,608;3,006,759; 3,062,653; 3,214,437; 3,253,924; 3,311,476; 3,419,391;3,419,808; 3,476,560; 3,582,322, etc. Also as a cyan dye forming couplerthere are phenol type couplers, naphthol type couplers, etc., asdisclosed in U.S. Pat. Nos. 2,474,293; 2,698,794; 3,034,892;

23 3,214,437: 3,253,924; 3.31 L476; 3,582,322; 3,591,383; etc.

Each of these couplers can have at the active carbon atom of thecoupling position. replacing hydrogen atoms of the active carbon atom,an atom or group capable of being split off on oxidative coupling withan aromatic primary amine developing agent such as a halogen atom or anether, a thioether, an acyloxy. a phthalimido, a hydantoinyl, athiocyano, a sulfo, a sulfino, a saccharinyl, a benzotriazolyl, etc.,group. Also, the coupler can be a so-called colored coupler having achromophore such as a diazo group, a styryl group, etc., as asplitting-off group. Further the coupler can have a so-called diffusionresistant group so as to prevent diffusion of the coupler in theemulsion layers. Also the coupler can have a group such as a sulfogroup, a carboxy group, etc., for dispersing the coupler in a micellarstate as an alkali metal salt or an alkaline earth metal salt thereof.

As a dispersing agent for preparing the coupler dispersion and as acoating aid for applying each coating composition in the production ofthe light-sensitive material of the present invention, any known surfaceactive agent can be advantageously uses. For example, an anionic surfaceactive agent having a sulfonic acid, a sulfuric acid. a phosphoric acid,a carboxylic acid or a salt thereof; a nonionic surface active agenthaving a hydroxy group; a cationic surface active agent having anammonium, a phosphonium, an aniliniurn, a pyridinium, etc. group; and anamphoteric surface active agent having an anionic group and a cationicgroup in the same molecule; can be used.

The light-sensitive material of the present invention can be treated.after exposure, using known processing methods. For example, when thelight-sensitive material of the present invention is intended to use fora negative or a positive material of a nega-posi type system, thematerial can be treated using the following main steps:

I. Color development 2. Stop or fixing 3. Bleaching followed by fixing,or blixing Of these steps step 2 can be omitted. Also, if desired, ahardening step for hardening the photographic layer or a pretreatmentstep in an alkaline bath for removing a resin backing layer can be usedprior to step 1. Further. if desired, a hardening step can be employedbetween step 1 and step 2 or step 2 and step 3, or after step 3. Stillfurther, if desired, a stabilizing step for improving the stability ofthe images can be used. Moreover, washing steps can be used between eachof the steps or after the last step. After all of the processing stepsare finished, the photographic material is dried. Suitable dryingmethods which can be used are natural dyring by allowing the material tostand in the air, heat drying, hot-air drying, drying with an infraredradiation, a drying with an electron beam, or any other known methods.

When the light-sensitive material of the present invention is intendedto be used for a material of a reversal type system, the material can betreated using the following main steps:

I. Black and white development 2. Reversal exposure 3. Color development4. Stop or fixing 5. Bleaching followed by fixing, or blixing Of thesesteps step 2 can be omitted when the color developer solution for step 3contains a fogging agent. In reversal processing, a hardening step, analkaline pre-bath step, a stabilizing step, a washing step can be, ifdesired, employed before or after each step described above, as in theabove described nega-posi type processing step. Also after finishing allof the processing steps, the photographic material is dried in the samemanner as described in the nega-posi type processing step.

For each step of the above described nega-posi type processing and thereversal type processing, processing baths of known compositions can beused.

A suitable color developer solution is an alkaline solution containing acolor developing agent. As the color developing agent, any knownaromatic primary amino developing agent can be used, for example,phenylene diamines such as N,N-diethyl-paraphenylene diamine,N-ethyl-N-hydroxyethyl-para-phenylene diamine, N-ethyl-N-hydroxyethyl-2-methyl-para-phenylene diamine,N-ethyl-N-B-methanesulfonamidoethyl3-methyl-4-aminoaniline,N,N-diethyl-2-methyl-paraphenylene diamine,N-ethyl-N-ethoxyethyI-Z-methylpara-phenylene diamine, and the sulfates,hydrochlorides, sulfites, oxalates, etc. of these compounds. The colordeveloper solution can further contain conventional additives such as asulfate, a carbonate, a bisulfite, a bromide or an iodide of an alkalimetal, benzyl alcohol, a water softener (such as sodiumhexametaphosphate, an alkali metal hydroxide, hydroxylamine, a sulfateor a hydrochloride of hydroxylamine, etc.), a competing coupler (such asmono sodium l-amino-S- naphthol-3.6-disulfonate, citrazinic acid, etc.),if desired. Also the color developer solution can contain a foggingagent (such as N-butylamine, an alkali metal salt of borohydride,ethylene-diamine, etc.), when it is used as color developer for reversaltype processing.

As the stop solution, a solution containing any known pH-reducing agent(such as acetic acid, phthalic acid, etc.) can be used.

As the fixing solution, a solution containing any known fixing agent(such as sodium thiosulfate, ammonium thiosulfate, potassiumthiocyanate, etc.) can be used.

As the bleaching solution, a solution containing any known belachingagent (such as a ferricyanide, a bichromate, a ferric salt ofethylene-diamine tetraacetic acid, etc.) can be used.

When the bleaching step and the fixing step are carried out in a monobath, a solution containing any known silver halide solvent and anyknown silver oxidizing agent can be used. Examples of such silver halidesolvents are a thiosulfate, a thiocyanate, an organic diol containing anoxygen atom or a sulfur atom (such as 3-thiol ,5-pentanediol,3,6-dithial ,8-octanediol, 9- oxa-3,6, l 2, l S-tetrathia-l,l7-heptadecanediol, etc. a sulfur-containing organic dibasic acid or asalt thereof (such as ethylenebisthioglycolic acid, a sodium saltthereof, etc.), imidazolidinethione, and the like. Also examples ofsilver oxidizing agents are a ferricyanide, a quinone, a ferric salt. acupric salt, a cobaltic salt, a complex salt of an ammonium ion or analkali metal ion, and a ferric ion, a cupric ion or a cobalt ion, and anorganic acid (examples of the organic acids are malonic acid, tartaricacid, ethylmalonic acid. malic acid, fumaric acid, diglycolic acid,dithioglycolic acid, ethyliminopropionic acid, nitrilotriacetic acid,ethyl- 25 enediamine tetraacetic acid, aminotriacetic acid,ethylenedithioglycolic acid. dithioglycolic acid. etc. or a chelatecompound of ferric ion. cupric ion or a cobalt ion (examples of ligandsof the chelate compounds are ethylenediamine, diethylenetriamine.triethylenetetraamine, diaminopropane, diaminocyclohexane.polyethyleneimine, acetylacetone, diethyldithiocarbamate, oxyquinoline,dithiozone. dipyridyl, phenanthrenine, etc.), and the like.

The couplers of the present invention can be used, in addition to theabove described multi-layer photographic materials based on substractivethree color system, in any silver halide light-sensitive materials whichcan form dye images by color development using an aromatic primary aminodeveloping agent, such as color radiographic photographic materials,infrared-sensitive photographic materials, photographic materials forrecording radar images, color micro-photographic materials, and thelike.

The invention will now be explained in greater detail by reference tothe following examples.

EXAMPLE 1 A mixture of 3.0 g or Coupler lX (a yellow color formingcoupler), 1.5 ml of di-n-butyl phthalate, 2.0 ml of ethyl acetate and0.15 g of sodium di(2-ethylhexyl)- B-sulfosuccinate was dissolved byheating to 60C and mixed with 25 ml of an aqueous solution at 40Ccontaining 2.0 g of gelatin, and the mixture was stirred using a highspeed mixer at 50C for 10 minutes to prepare a fine dispersion of thecoupler.

The coupler dispersion was mixed with l50 g of a photographic emulsioncontaining 47 millimoles of silver iodobromide and 10 g of gelatin, andthen 2 ml of a 1 percent aqueous solution of4-hydroxy-6-methyll.3,3a.7-tetraazaindene, 5 ml of a 2 percent aqueoussolution of the sodium salt of Z-hydroxy-4,6-dichloro-striazine and 2 mlof a 5 percent aqueous solution of saponin were added in order. Themixture was coated on a cellulose acetate film base in a dry thicknessof 5 microns. On the emulsion layer, a gelatin layer of a dry thicknessof 1 micron was coated as a protective layer.

The film was subjected to stepwise exposure for sensitometry andprocessed in the following steps.

CH O- Q-COCH CONH- The composition of the processing solutions used wereas follows.

Color Developing Solution l (pH 105) Water 1000 mlZ-Amino-S-diethylaminotoluene 2.5 g Hydrochloride Sodium Sulfite(anhydrous) 5 g Sodium Carbonate (monohydrate) 47 g Potassium Bromide 2g Fixing Solution (2H 4.2) Water l000 ml Sodium Thiosulfate(pentahydrate) 80 g Sodium Sulfite (anhydrous) 5 g Borax 6 g GlacialAcetic Acid 15 g Chromium Alum 7 g Bleaching Solution (EH 7.2) Water1000 ml Potassium Ferricyanide [7 g Borax 5 g Potassium Bromide 7 gAfter processing and drying, the film provided clear yellow dye imageshaving an absorption maximum at 448 millimicrons.

EXAMPLE 2 A solution prepared by heating to 80C a mixture of 7 g ofCoupler ill (a yellow color forming coupler), 3.5 ml of di-n-butylphthalate. 7 ml of n-butyl acetate and 0.1 g of sorbitan monolaurate wasadded I20 g of an aqueous solution at 50C containing 10 g of gelatin and0.5 g of sodium triisopropylnaphthalene sulfonate (Alkanol B made by E.l. du Pont de Nemous, U.S.A.) and the mixture was passed 5 times througha pre-heated colloid mill to prepare a fine dispersion of the coupler.

All of the coupler dispersion collected by washing the colloid mill withcc of a warm water was mixed with 320 g of a photographic emulsioncontaining 0. l 0 moles of silver iodobromide and 21.3 g of gelatin. andthen 5 ml of a 3 percent acetone solution of triethylene phosphamide wasadded. The mixture was coated on a baryta coated paper laminated withpolyethylene in a dry thickness of 4 microns and dried.

For comparison, a film was prepared by earring out the same proceduresas described above except that 7 g of a coupler having the followingstructure was used.

Comparison Coupler (a) Melting Point 955C Comparison Coupler (a) had thesame structure as that of Coupler Ill except for the oil-solublediffusion resistant group, and was prepared according to the methoddescribed in US. Pat. No. 2,908,573.

These two film samples were subjected to stepwise exposure forsensitometry and processed in the following steps.

Processing Step Temperature Time 1 Color Development 6 minutes I-Continued 3. Blixing 4. Wash 5 5. Stabilizing Bath 30 seconds Thecompositions of the processing solutions used were as follows.

Color Developer Solution 11 (pH 10.7)

Water 1000 ml Benzyl Alcohol 120 ml Sodium Hexarnetaphosphate 2.0 gSodium Sulfite (anhydrous) 2.0 g Sodium Carbonate (monohydrate) 27.5 gHydroxylamine Sulfate 2.5 g 4-Amino-3-methyl-N-ethyl-N-(B- 4.() g

methanesulfonamidoethyl )aniline Sesquisulfate Monohydrate Stop SolutionAfter processing and drying, the color paper containing Coupler 111 andthe sample containing Comparison Coupler (21) provided yellow dye imageshaving an absorption maximum at 449 and 451 microns, respectively.

These color papers having dye images were stored in the dark at 60C and75 percent relative humidity for 20 days and the fading of the imageswas measured. The results obtained are shown in the following table.

Rate of Fading (Rate of density after storage against the initialdensity 1) Sample lnitial Density Coupler Ill of the Present lnvention12 Comparison Coupler (a) 21 18 As can be seen from the results in thetable, the dye images formed according to the present invention usingCoupler 111 have improved stability to heat and humidity, than the dyeimages formed from the light-sensitive material containing knownComposition Coupler (a).

EXAMPLE 3 A solution prepared by heating to 65C a mixture of 10 g ofCoupler XXV (a magenta color forming coupler), 5 g of tricresylphosphate, 0.6 g of di-(Z- ethylhexyl)-B-sulfosuccinate and 5 ml ofethyl acetate was mixed with g of a 7 percent gelatin solution. and themixture was stirred vigrorously using a high speed mixer for 10 min. toprepare a fine dispersion of the coupler.

50 g of the coupler dispersion was mixed with 170 g of a photographicemulsion containing 60 millimoles of silver iodobromide and 12 g ofgelatin, and 5 ml of a 3 percent methanol solution of triethylenephosphamide was added. The mixture was coated on a cellulose acetatefilm base in a dry thickness of 5 microns and on the emulsion layer agelatin layer having a dry thickness of 1 micron was coated as aprotective layer and dried.

For comparison, a film was prepared by carrying out the same proceduresas described above except that 8.7 g of a coupler having the followingstructure was used.

NBC 00 H O Comparison Coupler (B) Melting Point l77-l 78C ComparisonCoupler (B) has the same structure as that of Coupler XXV except for theoil-soluble diffusion resistant group.

These two film samples were subjected to stepwise exposure forsensitometry and processed as described in Example 1, except for using acolor developer solution having the following composition.

Color Developer Solution lll (pH Water 1000 ml Benzyl Alcohol 3.8 mlSodium Sulfite (anhydrous) 2.0 g Sodium Hydroxide 1N solution) 14 ml 4Amino-3methyl-N-ethyl-N-B- 5.0 g metha nesulfonamidoethyl )anilineSesquisulfate Monohydrate Potassium Bromide 1.0 g Sodium Carbonate(monohydrate) 50.0 g

After processing and drying, both films provided magenta dye imageshaving the spectral absorption characteristics shown in the followingtable.

Spectral Absorption Characteristics Ratio of a density at a wavelength60 mp longer than the absorption maximum wavelength in the absorptionmaximum density.

As is shown in the above table, the color lightsensitive materialaccording to the present invention containing Coupler XXV can provide aspectral absorption curve of a sharply cut form in comparison with thelight-sensitive material containing known Comparison Coupler (B). Themagenta dye image having such spectral absorption characteristicsprovides colors of high purity. especially a red color. in colorreproduction based on the subtractive photographic system.

EXAMPLE 4 Using six kinds of 5-methyl-4,o-dichlorophenol type 5 CouplerXL (at cyan color forming coupler), l g of 2- lbenzotriazolyl-S-n-amylphenol, l 1 ml of di-n-butyl phthalate. 0.2 g orsorbitan monolaurate and l5 ml of ethyl acetate and 150 ml of a gelatinsolution containing g of gelatin and 0.4 g sodiumdodecylbenzenesulfonate were stirred vigorously in a high speed mixer at50C for 10 minutes to prepare a dispersion of the couplers in which theaverage diameter of the oil drop let containing the coupler was 0.2microns. All of the coupler dispersion collected by washing the mixerwith 200 ml of a warm water was added to 250 g of aphotodichloro-s-triazine was added. The mixture was coated on a paperlaminated on both surfaces with polyethylene in a dry thickness of 2.5microns, and on the emulsion layer a gelatin layer having a drythickness of l micron was coated and dried. This film was designatedSample (4-1).

Using the same procedures as described above except for using each ofthe couplers shown in the following table. five additional kinds offilms were prepared.

Film Sample No. Comparison Coupler Amount Used 4-2 Compound A 4.7 g

These six color printing papers were subjected to stepwise exposure forsensitometry and processed as described in Example 2 to provide cyan dyeimages.

These samples having cyan dye images were stored under the conditionsset forth in the following table for enforced fading testing. Theresults obtained are shown in the following table.

From these results it can be understood that the cyan dye images formedaccording to the present invention are more stable to fading due to heatand humidity. particularly to heat fading under dry conditions. than thecyan dye images formed from known couplers having similar structures.This fact illustrates that the color photographic images formed from thelightsensitive material of the present invention are more stable thanthose formed from conventionally known couplers, and can be stored for along period of time.

EXAMPLE 5 A color printing paper was prepared according to the followingprocedures. Coating Solution 1 and Coating Solution 2 weresimultaneously coated on a surface of a paper laminated on both sideswith polyethylene using a slit hopper as described in U.S. Pat. No.2,761,419. Coating Solution 1 and Coating Solution 2 were coated inorder on the support and the dry thickness of each layer was 2.5 and 1.0micron, respectively. Then Coating Solutions 3,4,5 and 6 were coated, inorder, on the coating described above using the same slit hopper. Thedry thickness of each layer was 3.0, 2.0, 2.0 and 1.0 micron,respectively.

Coating Solution l A mixture of 24 g of Coupler XIII (a yellow colorforming coupler), 18 g of di-n-butyl phthalate and ml of ethyl acetatewas dissolved by heating to 50C, the solution thus obtained was added to600 ml of an aqueous solution containing 40 g of gelatin and 1.5 g ofsodium dodecylbenzene sulfonate and then the mixture was passed 3 timesthrough a homogenizer to prepare a coupler dispersion.

All of the coupler dispersion was added to 500 g of a photographicemulsion containing 0.] mole of silver chlorobromide (bromide content:mole percent, average grain size: 0.8 p.) and 40 g of gelatin, and then60 mg of 5-methyl-6-hydroxyl .3,4-triazaindene and 20 ml of a 3 percentmethanol solution of triethylene phosphamide was added.

Coating Solution 2 A mixture of 5 g of n-pentadecylhydroquinone. l5 g ofdi-n-butylphthalate and I ml of ethyl acetate was dissolved by heatingto 50C. the solution thus obtained was added to l.000 ml of an aqueoussolution containing 70 g of gelatin. 0.8 g of sodium dodecylbenzenesulfonate and 0.l g of sodium bisulfite. and then the mixture was passed3 times through a homogenizer to prepare a dispersion. To the dispersionl .500 ml of water, L000 ml of a 2 percent aqueous solution of thepotassium salt of poly-p-sulfostyrene and 20 ml of a 3 percent methanolsolution of triethylene phosphamide was added.

Coating Solution 3 A mixture of 23 g of Coupler XXVlll (a magenta colorforming coupler), 1.5 g of 2.5-di-tertoctylhydroquinone, l.5 g of4.4.4',4'-tetramethyl-6.6'- dihydroxy-7.7'-dimethoxy-2,2-spirochroman,20 g of tri-o-cresyl phosphate and 50 ml of ethyl acetate was dissolvedby heating to 50C and the solution thus obtained was added to 600 ml ofan aqueous solution containing 40 g of gelatin and L5 g of sodiumpdodecylbenzene sulfonate. and then the mixture was passed 3 timesthrough a homogenizer to prepare a coupler dispersion.

All of the coupler dispersion was added to l .000 g of a green-sensitivephotographic emulsion containing 0.2 moles of silver chlorobromide(bromide content: 40 mole percent, average grain size: 0.25 14) and 90 gof gelatin. and then 120 mg of 5methyl-6-hydroxy-l ,3.4- triazaindeneand 40 ml of a 3 percent methanol solution of triethylene phosphamidewas added.

Coating Solution 4 A mixture of 5 g of2-benzotriazolyl-4-tertbutylphenol. g of2-benzotriazolyl-4-tert-butyl-6- iso-butylphenol, 5 g of2.5-di-tert-octylhydroquinone, 35 g of di-n-butyl phthalate and 50 ml ofethyl acetate was dissolved by heating to 50C and the solution thusobtained was added to 750 ml of an aqueous solution containing 50 g ofgelatin, I.8 g of sodium pdodecylbenzene sulfonate and 0.1 g of sodiumbisulfite. and then the mixture was passed 3 times through a homogenizerto prepare a dispersion.

All of the dispersion was mixed with 750 ml of an aqueous solutioncontaining 50 g of gelatin and 30 ml of a 3 percent methanol solution oftriethylene phosphamide.

Coating Solution 5 A mixture of 17 g Coupler XL (a cyan color formingcoupler), g of di-n-butyl phthalate and 40 ml of ethyl acetate wasdissolved by heating to 50C and the solution thus obtained was added to600 ml of an aqueous solution containing 40 g of gelatin and L5 g ofsodium p-dodecylbenzene sulfonate and then the mixture was passed 3times through a homogenizer to prepare a coupler dispersion.

All of the coupler dispersion was added to 500 g of a red-sensitivephotographic emulsion containing 0.1 mole of silver chlorobromide(bromide content: 40 mole percent, average grain size: 0.25 p) and 45 gof gelatin, and then 60 mg of 5-methyl-6-hydroxy-l .3,4- triazaindeneand ml of a 3 percent methanol solution of triethylene phosphamide wasadded.

Coating Solution 6 To 1.000 ml of an aqueous solution containing 40 g ofgelatin. there were added l50 ml of a 2 percent aqueous solution of thepotassium salt of poly-psulfostyrene. 20 ml of a 2 percent aqueoussolution of sodium p-dodecylbenzene sulfonate and 50 ml of a 3 percentmethanol solution of triethylene phosphamide.

The color printing paper thus prepared was exposed through a colornegative image and subjected to the color developing treatment asdescribed in Example 2. A clear color print comprising a yellow dyeimage hav' ing an absorption maximum at 442 mp. a magenta dye imagehaving an absorption maximum at 540 mp. and a cyan dye image having anabsorption maximum at 665 my. and having a maximum blue light density of2.45. a maximum green light density of 2.55 and a maximum red lightdensity of 2.40 was obtained.

EXAMPLE 6 A mixture of IO millimoles of a coupler of the presentinvention (as shown in the following table). 5.0 g of a high boilingcoupler solvent and 10 ml of ethyl acetate was dissolved at refluxingand the solution was added to ml of an aqueous solution containing 0.5 gof pdodecylbenzene sulfonate and I0 g of gelatin and then the mixturewas stirred vigorously using a homoblender to prepare a fine dispersionof the coupler.

All ofthe coupler dispersion was mixed with 400 g of a photographicemulsion containing 0.] mole of silver iodobromide (iodide content: 3mole percent, average grain size: 0.4 microns) and 35 9 of gelatin andthen 12.0 ml of a 3 percent methanol solution of triethylene phosphamideand 500 cc of water were added. The mixture of each dispersion thusprepared was coated on a transparent cellulose acetate film base in adry thickness of 6.0 microns to prepare films.

These films were subjected to stepwise exposure for sensitometry andprocessed in the same manner as described in Example I using 2-amino-5-diethylaminotoluene as a color developing agent. Dye images having theabsorption maximum shown in the following table were obtained.

-Cntinued Coupler Coupler Solvent Absorption Maximum Wavelength of Dyelmage XXVlll TCP 545 XXIX THP 544 XXX TCP 543 XXX! 550 XXX" 550 XXXlll551 XXXlV 539 XXXVI 546 XXXVII DB? 710 XXXlX 676 XL 675 XLl 674 XL" 666XLlll 71 l XLlV 712 DPB: Di-n-hutyl phthalatc TC P: Tri-o-cresylphosphate THP: Trim-hcxyl phosphate EXAMPLE 7 3.00 mg ofa cyan dye (MP.139C, A,,,,, 659 mp1. e=3 1,500) which was obtained by the coupling ofCoupler A (a phenol type cyan coupler) with N,N-diethyl-para-phenylenediamine using silver chloride as an oxidizingagent in an alkaline condition. 3.00 mg a coexisting coupler and 100 muof di-nbutyl phthalate (DBP) were placed into a brown colored glassampoule of a volume of 0.8 ml (0.5 X 4.0 cm) to protect from light andhumidity, and the contents were dissolved by vibrating. The ampoule wasdipped into an oil bath at a controled temperature of 110 1' 0.2C androcked for -30 hours. Then the ampoule was opened and the amount ofremaining dye was spectrometrically determined in methanol.

The influence of various coexisting couplers to the ratio of remainingdye is shown in the following table. la the table, the ratio of theremaining dye was illustrated using the rate of decrease in theabsorption coefficient against that of the fresh dye.

ln the above experiments the couplers and DB? of high purity which hadbeen purified in a conventional manner were used. Also the glassampoules were washed with a chromic acid mixture. then with water vaporand dried.

Variation of Coexisting Coupler Ratio of Remaining Dye Control (withoutcoupler) 94.6 Coupler A 49.9 Coupler D 84.2 Coupler G 52.0 Coupler H83.7 Coupler XXXIX 93. l Coupler XL 92.8 Coupler XLI 91.7

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:

l. A color photographic light-sensitive material which comprises asupport having thereon at least one silver halide emulsion layercontaining a coupler represented by the general formula CE I 3 (R QNHCOC 0- wherein 0 represents a coupler residue forming a dye uponreaction with an oxidation product of an aromatic primary aminodeveloping agent; R represents an alkyl group, an aralkyl group. analkoxy group, an alkoxyalkyl group, an acylamido group or analkoxycarbonyl group, each having from 4 to 20 carbon atoms; R,represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkylgroup having from I to 5 carbon atoms or an alkoxy group having from Ito 5 carbon atoms; In represents an integer of l to 4; n represents aninteger of l to 4; and the sum of m n is 2 to 5; and R and R: can form anon-metallic atom-containing five membered ring or a six membered ring.

2. The color photographic light-sensitive material as claimed in claim1, wherein said coupler has the general formula (I315 2 Q-NHCOC owherein Q, R, and R are as defined in claim 1.

3. The color photographic light-sensitive material as claimed in claim1, wherein m is 1 and n is l and 0, R and R are as defined in claim I.

4. The color photographic light-sensitive material as claimed in claim1, wherein said coupler has the general formula 1 i Q NHCOC wherein Q,R, and R are as defined in claim 1.

5. The color photographic light-sensitive material as claimed in claim2, wherein R represents a hydrogen atom. a chlorine atom, a methyl groupor a methoxy group.

6. The color photographic light-sensitive material as claimed in claim3, wherein R represents a hydrogen 35 36 atom. a chlorine atom. a methylgroup or a methoxy group.

7. The color photographic light-sensitive material as claimed in claim2, wherein a total number of carbon atoms included in the R /N C CH 2 R-n l 5 R 14 l -NHCOC-O 1 C-CH-X g l (3H moiety is from M to 42. Y

8. The color photographic light-sensitive material as 15 claimed inclaim 4, wherein a total number of carbon N c NH atoms included in the nl (i3 CH X CH 1 5 R1 0' -NHCOCl O 2 CH /N c NHCONH moiety IS from 14 to42. R1 N 9. The color photographic light-sensitive material as Ll Iclaimed in claim 1, wherein Q represents an C CH X acylacetanilide. acyanoacetophenone, a S-pyrazolone, ll :1 phenol or a l-naphthol couplerresidue. 0

10. The color photographic light-sensitive material as claimed in claim1, wherein Q represents a coupler residue having the formula R NN=C-1\HCO@ 14 I Qcoclmcomi fi 0H X X 0 R y 40 N I a C C5 X g -COZHCONHQ15 X 0H 12 Y 1? T QO-CII-COCHCORH-Q x R 011 x R 1 CH CON 8 CB-i-COCiI-ECONH- wherein R represents a monovalent atom or group selectedfrom the group consisting of a hydrogen atom, a halogen atom. an alkylgroup. an alkoxy group. an amino group or an acylamino group; R isbonded to the 3-position, 4-position or 5-position of the anilide ringand represents a hydrogen atom or a monovalent group selected from thegroup consisting of a halogen atom. a cyano group. a carbamoyl group. analkoxycarbony] group. a sulfamoyl group. an acylamino group, a nitrogroup. an alkyl group, an aryl group. an alkoxy group. an aryloxy group,an imido group. an alkylsulfonyl group or an arylsulfonyl group; Rrepresents an aryl group selected from the group consisting ofa phenylgroup substituted with a halogen atom. an alkyl group. an alkoxy group.an aryloxy group. a nitro group. a cyano group or an acylamino group; R,represents one or more monovalent atoms or groups selected from thegroup consisting of a hydrogen atom. a halogen atom, an alkyl group, analkoxy group or an aryloxy group; Ru; represents a monovalent groupselected from the group consisting of an alkyl group, an aryl group. analkoxy group, a carbamoyl group, an acylamino group, a ureido group. ananilino group or an alicyclic amino group; R represents one or moremonovalent atoms or groups selected from the group consisting of ahalogen atom, and alkyl group, an alkoxy group. an aryloxy group or anacylamino group; R represents a monovalent atom or group selected fromthe group consisting ofa hydrogen atom, an alkyl group or an aryl group;Rm represents a divalent group sea 38 lected from the group consistingof an alkylene group or an arylene group; X, represents a hydrogen atomor a coupling-off group which is split off on coupling with theoxidation product of an aromatic primary amino developing agent and isselected from the group consisting of a halogen atom, an alkoxy group,an aryloxy group. an acyloxy group, a sulfonyloxy group, a cyclicdiacylamino group, a cyclic sulfonylacylamino group; and Y represents ahydrogen atom, a halogen atom. an alkyl group, an alkoxy group, anaryloxy group or a N.N-dialkylamino group.

11. The color photographic light-sensitive material as claimed in claimI, wherein said coupler has the general formula Q rmcoc 0 CH C 5H5 (n) aphenol or a l-naphthol coupler residue.

1. A COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL WHICH COMPRISES SUPPORTHAVING THEREON AT LEAST ONE SILVER HALIDE EMULSION LAYER CONTAINING ACOUPLER REPRESENTED BY THE GENERAL FORMULA
 2. The color photographiclight-sensitive material as claimed in claim 1, wheRein said coupler hasthe general formula
 3. The color photographic light-sensitive materialas claimed in claim 1, wherein m is 1 and n is 1 and Q, R1 and R2 are asdefined in claim
 1. 4. The color photographic light-sensitive materialas claimed in claim 1, wherein said coupler has the general formula 5.The color photographic light-sensitive material as claimed in claim 2,wherein R2 represents a hydrogen atom, a chlorine atom, a methyl groupor a methoxy group.
 6. The color photographic light-sensitive materialas claimed in claim 3, wherein R2 represents a hydrogen atom, a chlorineatom, a methyl group or a methoxy group.
 7. The color photographiclight-sensitive material as claimed in claim 2, wherein a total numberof carbon atoms included in the
 8. The color photographiclight-sensitive material as claimed in claim 4, wherein a total numberof carbon atoms included in the
 9. The color photographiclight-sensitive material as claimed in claim 1, wherein Q represents anacylacetanilide, a cyanoacetophenone, a 5-pyrazolone, a phenol or a1-naphthol coupler residue.
 10. The color photographic light-sensitivematerial as claimed in claim 1, wherein Q represents a coupler residuehaving the formula
 11. The color photographic light-sensitive materialas claimed in claim 1, wherein said coupler has the general formula 12.The color photographic light-sensitive material as claimed in claim 11,wherein Q represents an acylacetanilide, a cyanoacetophenone, a5-pyrazolone, a phenol or a 1-naphthol coupler residue.